CN113754446A - 一种3d打印氮化硅纤维气凝胶及其制备方法与应用 - Google Patents

一种3d打印氮化硅纤维气凝胶及其制备方法与应用 Download PDF

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CN113754446A
CN113754446A CN202010491676.0A CN202010491676A CN113754446A CN 113754446 A CN113754446 A CN 113754446A CN 202010491676 A CN202010491676 A CN 202010491676A CN 113754446 A CN113754446 A CN 113754446A
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silicon nitride
nitride fiber
printing
fiber aerogel
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朱光达
侯仪
赵宁
徐坚
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Institute of Chemistry CAS
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Abstract

本发明公开一种3D打印氮化硅纤维气凝胶及其制备方法与应用。所述方法包括如下步骤：(1)含有硅源、碳源和高分子粘结剂的打印墨水，在氮气气氛下高温烧结，得到所述氮化硅纤维气凝胶；或者(1’)含有硅源、碳源和高分子粘结剂的打印墨水经3D打印，得到打印制件；所述打印制件在氮气气氛下高温烧结，得到所述氮化硅纤维气凝胶。所用原料简单廉价，制备过程简单，首次以打印墨水或直接墨水书写方式得到氮化硅纤维气凝胶，制备的氮化硅纤维气凝胶结构完整，可通过所述3D打印方法赋予复杂结构，并可以应用于阻燃、保温、隔热、吸附、传感器等诸多领域。

Description

一种3D打印氮化硅纤维气凝胶及其制备方法与应用
技术领域
本发明属于3D打印技术领域，具体涉及一种3D打印氮化硅纤维气凝胶及其制备方法与应用。
背景技术
气凝胶材料具有低密度、大比表面积、优异的隔热性能等优点，被广泛应用于保温隔热、污染物吸附、传感器等诸多领域。相比于颗粒或片层构筑单元的气凝胶，以纤维为基本单元构筑的气凝胶显示出了更低的密度和更大的比表面积。其中，聚合物纤维是常用来构筑纤维气凝胶的材料，然而聚合物本身耐热性较差，限制了纤维气凝胶的使用。虽然现有技术已开发了一系列基于无机陶瓷纤维的气凝胶材料，但其制备方法复杂，需严格控制反应气氛及前驱体组分，难以规模化应用。
氮化硅陶瓷具有高强度、低密度、耐高温等性质，是一种应用广泛的陶瓷材料。3D打印作为一项新兴的快速成型技术，能够一次成型得到复杂结构，现有技术中主要采用激光烧结或者光固化来制备致密的氮化硅陶瓷材料。目前尚未有3D打印制备氮化硅纤维气凝胶的报道。
发明内容
本发明提供了一种氮化硅纤维气凝胶的制备方法，所述方法包括如下步骤：
(1)含有硅源、碳源和高分子粘结剂的打印墨水，在氮气气氛下高温烧结，得到所述氮化硅纤维气凝胶；
或者(1’)含有硅源、碳源和高分子粘结剂的打印墨水经3D打印，得到打印制件；所述打印制件在氮气气氛下高温烧结，得到所述氮化硅纤维气凝胶。
根据本发明的实施方案，所述硅源可以选自以下材料中的至少一种：气相二氧化硅、纳米二氧化硅、微米二氧化硅、玻璃粉和聚硅氧烷等；优选地，所述硅源为气相二氧化硅和/或玻璃粉。
根据本发明的实施方案，所述碳源可以选自以下材料中的至少一种：石墨烯、碳黑、碳纳米管、富勒烯、石墨炔等；优选地，所述碳源为石墨烯、碳黑和碳纳米管中的至少一种。
根据本发明的实施方案，所述高分子粘结剂包括高分子材料和溶剂。
根据本发明的实施方案，所述高分子材料选自热塑性高分子材料，优选选自以下材料中的至少一种：聚乙烯、硅树脂、聚丙烯、聚乙烯醇、聚苯乙烯、聚丁二烯、聚甲基丙烯酸甲酯等；示例性为聚乙烯醇、聚甲基丙烯酸甲酯和/或聚苯乙烯。
根据本发明的实施方案，所述溶剂可以选自以下材料中的至少一种：水、乙醇、乙酸乙酯、二氯甲烷、正己烷、石油醚、甲苯、二甲苯、丙酮、四氢呋喃、氯仿、N,N-二甲基甲酰胺等；优选为水和/或丙酮。
根据本发明的实施方案，所述高分子粘结剂中，溶剂与高分子材料的质量比为100:(0.1-30)，优选为100:(5-25)，示例性为100:10、100:20、100:30。
根据本发明的实施方案，所述高分子材料与硅源和碳源的质量之和的质量比为(0.1-5):100，优选为(0.5-3):100，示例性为0.5:100、1:100、2:100、3:100、4:100、5:100。
根据本发明的实施方案，所述碳源与所述硅源的质量比为(1-10):(1-10)，优选为(1-5):(1-5)，示例性为1:1、4:5、5:4。
根据本发明的实施方案，所述氮气气氛可以选自普氮或高纯氮。
根据本发明的实施方案，步骤(1’)中，所述3D打印为直接书写3D打印。
根据本发明的实施方案，所述高温烧结的温度为1300-1800℃，例如1400-1600℃，示例性为1300℃，1400℃，1500℃，1600℃，1700℃，1800℃。
根据本发明的实施方案，所述高温烧结的时间为1-12h，例如3-8h，示例性为4h、5h、6h、7h。
根据本发明的实施方案，所述高温烧结的升温速率为1-20℃/min，例如为3-10℃/min，示例性为3℃/min，4℃/min，5℃/min。
根据本发明的实施方案，所述高温烧结的升温速率或降温速率相同，例如为1-10℃/min，比如2-8℃/min；或者降温时随炉冷却。
上述制备过程基于如下反应：
SiO2(固)+C(固)＝SiO(气)+CO(气) (a)
3SiO(气)+C(固)+2N2(气)＝Si3N4(固)+3CO(气) (b)
6SiO(气)+4N2(气)＝2Si3N4(固)+3O2(气) (c)
本发明还提供由上述方法制备得到的氮化硅纤维气凝胶。
根据本发明的实施方案，所述氮化硅纤维气凝胶的密度为0.01～300mg/cm3，优选0.1～50mg/cm3。
根据本发明的实施方案，所述氮化硅纤维的直径为10-500nm，例如20-300nm，又如50-100nm。
根据本发明的实施方案，所述氮化硅纤维表面上附着少量所述硅源和/或碳源。
根据本发明的实施方案，所述氮化硅气凝胶具有基本如图2或图4所示的形貌。
本发明还提供所述氮化硅纤维气凝胶在阻燃、保温、隔热、吸附或传感器等领域中的应用。
本发明的有益效果：
本发明提供了一种氮化硅纤维气凝胶及其制备方法与应用，所用原料简单廉价，制备过程简单，首次以打印墨水或直接墨水书写方式得到氮化硅纤维气凝胶，制备的氮化硅纤维气凝胶结构完整，可通过所述3D打印方法赋予其复杂结构，并可以应用于阻燃、保温、隔热、吸附、传感器等诸多领域。
附图说明
图1为实施例1中氮化硅纤维气凝胶的照片。
图2为实施例1中氮化硅纤维气凝胶的扫描电镜图。
图3为实施例1中氮化硅纤维气凝胶被酒精灯灼烧前后的照片。
图4为实施例2中直接书写打印制件的过程及制件照片。
图5为实施例2中氮化硅纤维气凝胶的扫描电镜图。
图6为实施例2中氮化硅纤维气凝胶的热失重曲线。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品。
实施例1
1)将5g水、1g聚乙烯醇、50g石墨烯和50g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)所得打印墨水放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以3摄氏度/分钟升温至1500摄氏度，保温4h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
图1为实施例1中氮化硅纤维气凝胶材料的照片，可以看出氮化硅纤维气凝胶整体呈白色，具有良好的可弯曲能力。
图2为实施例1中氮化硅纤维气凝胶材料的扫描电镜图，可以看出气凝胶材料以纤维结构为单元，纤维直径为几十纳米左右。
图3为实施例1中氮化硅纤维气凝胶被酒精灯灼烧的照片，可以看出氮化硅纤维气凝胶在酒精灯外焰中不发生燃烧(灼烧时间3分钟)，灼烧前后其形貌完全不变，说明了其优异的阻燃性和耐热性。
实施例2
1)将5g水、1g聚乙烯醇、40g石墨烯和50g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以4摄氏度/分钟升温至1500摄氏度，保温4h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
图4为实施例2中直接书写打印制件的打印过程及所得制件照片，可以看出打印制件呈黑色，可获得多种的不同打印结构。
图5为实施例2中氮化硅纤维气凝胶材料的扫描电镜图，可以看出气凝胶材料以纤维结构为单元，纤维直径为几十纳米左右，纤维表面附着少量气相二氧化硅纳米颗粒。
图6为实施例2中氮化硅纤维气凝胶的热失重曲线，可以发现在整个加热过程中氮化硅纤维气凝胶的质量基本保持不变，体现了气凝胶材料具有良好的耐热性。
实施例3
1)将5g丙酮、0.5g聚甲基丙烯酸甲酯、50g石墨烯和50g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以4摄氏度/分钟升温至1600摄氏度，保温5h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
实施例4
1)将5g丙酮、0.5g聚甲基丙烯酸甲酯、50g石墨烯和40g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以5摄氏度/分钟升温至1400摄氏度，保温5h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
实施例5
1)将5g丙酮、0.5g聚苯乙烯、50g石墨烯和40g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以5摄氏度/分钟升温至1400摄氏度，保温5h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
实施例6
1)将5g丙酮、0.5g聚苯乙烯、50g碳黑和50g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以5摄氏度/分钟升温至1400摄氏度，保温6h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
实施例7
1)将5g丙酮、0.5g聚苯乙烯、50g碳纳米管和50g气相二氧化硅研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以5摄氏度/分钟升温至1400摄氏度，保温6h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
实施例8
1)将5g水、1g聚乙烯醇、40g碳纳米管和50g玻璃粉研磨分散，得到打印墨水；
2)将步骤1)中所得墨水放入直接书写打印机的注射器内，设定程序，随后打印出所设计的制件；
3)将步骤2)所得打印制件放置于坩埚内，并放入高纯氮气气氛保护的管式炉内，以4摄氏度/分钟升温至1500摄氏度，保温4h，随炉冷却，取出坩埚即可得到氮化硅纤维气凝胶材料。
实施例3-8得到的氮化硅纤维气凝胶材料具有与实施例1和实施例2相同的结构、形貌以及阻燃性和耐热性。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种氮化硅纤维气凝胶的制备方法，其特征在于，所述方法包括如下步骤：
(1)含有硅源、碳源和高分子粘结剂的打印墨水，在氮气气氛下高温烧结，得到所述氮化硅纤维气凝胶；
或者(1’)含有硅源、碳源和高分子粘结剂的打印墨水经3D打印，得到打印制件；所述打印制件在氮气气氛下高温烧结，得到所述氮化硅纤维气凝胶。
2.根据权利要求1所述的制备方法，其特征在于，所述硅源选自以下材料中的至少一种：气相二氧化硅、纳米二氧化硅、微米二氧化硅、玻璃粉和聚硅氧烷；优选地，所述硅源为气相二氧化硅和/或玻璃粉。
3.根据权利要求1或2所述的制备方法，其特征在于，所述碳源选自以下材料中的至少一种：石墨烯、碳黑、碳纳米管、富勒烯和石墨炔；优选地，所述碳源为石墨烯、碳黑和碳纳米管中的至少一种。
4.根据权利要求1-3任一项所述的制备方法，其特征在于，所述高分子粘结剂包括高分子材料和溶剂；
优选地，所述高分子材料选自热塑性高分子材料，优选选自以下材料中的至少一种：聚乙烯、硅树脂、聚丙烯、聚乙烯醇、聚苯乙烯、聚丁二烯、聚甲基丙烯酸甲酯；更优选为聚乙烯醇、聚甲基丙烯酸甲酯和/或聚苯乙烯；
优选地，所述溶剂选自以下材料中的至少一种：水、乙醇、乙酸乙酯、二氯甲烷、正己烷、石油醚、甲苯、二甲苯、丙酮、四氢呋喃、氯仿和N,N-二甲基甲酰胺；优选为水和/或丙酮；
优选地，所述高分子粘结剂中，溶剂与高分子材料的质量比为100:(0.1-30)；
优选地，所述高分子材料与硅源和碳源的质量之和的质量比为(0.1-5):100。
5.根据权利要求1-4任一项所述的制备方法，其特征在于，所述碳源与所述硅源的质量比为(1-10):(1-10)，优选为(1-5):(1-5)。
6.根据权利要求1-5任一项所述的制备方法，其特征在于，步骤(1’)中，所述3D打印为直接书写3D打印。
7.根据权利要求1-6任一项所述的制备方法，其特征在于，步骤(1’)中，所述高温烧结的温度为1300-1800℃，优选1400-1600℃。
优选地，所述高温烧结的时间为1-12h，优选3-8h。
优选地，所述高温烧结的升温速率为1-20℃/min，优选为3-10℃/min。
优选地，所述高温烧结的升温速率或降温速率相同，优选为1-10℃/min或者降温时随炉冷却。
8.一种氮化硅纤维气凝胶，其是通过权利要求1-7任一项所述方法制备得到的。
9.根据权利要求8所述的氮化硅纤维气凝胶，其特征在于，所述氮化硅纤维气凝胶的密度为0.01～300mg/cm3，优选0.1～50mg/cm3；
优选地，所述氮化硅纤维的直径为10-500nm，优选20-300nm；
优选地，所述氮化硅纤维表面上附着少量权利要求2中所述硅源和/或权利要求3中所述碳源；
优选地，所述氮化硅气凝胶具有基本如图2或图4所示的形貌。
10.权利要求8或9所述氮化硅纤维气凝胶在阻燃、保温、隔热、吸附或传感器领域中的应用。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890425A (zh) * 2022-04-02 2022-08-12 西安交通大学 一种多级结构弹性碳化硅纳米线气凝胶及其3d打印制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446501A (zh) * 2013-09-16 2015-03-25 中国科学院上海硅酸盐研究所 一种氮化硅陶瓷纤维的制备方法
CN108085785A (zh) * 2018-01-15 2018-05-29 中钢集团洛阳耐火材料研究院有限公司 一种氮化硅纤维材料的制备方法
CN108328586A (zh) * 2018-03-01 2018-07-27 西安交通大学 一种可压缩回复的氮化硅气凝胶及其制备方法
CN109553395A (zh) * 2018-12-28 2019-04-02 西安交通大学 一种陶瓷气凝胶的低成本制备方法
CN109704781A (zh) * 2018-12-28 2019-05-03 西安交通大学 一种氮化硅纳米带气凝胶及其制备方法
WO2020046687A1 (en) * 2018-08-31 2020-03-05 3M Innovative Properties Company Additive manufacturing method for making non-oxide ceramic articles, and aerogels, xerogels, and porous ceramic articles
CN110982111A (zh) * 2019-12-16 2020-04-10 中国科学院苏州纳米技术与纳米仿生研究所 3d打印芳纶气凝胶、其制备方法及应用
CN111004541A (zh) * 2019-12-24 2020-04-14 中国科学院苏州纳米技术与纳米仿生研究所 二氧化硅气凝胶纤维的3d打印墨水及3d打印制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446501A (zh) * 2013-09-16 2015-03-25 中国科学院上海硅酸盐研究所 一种氮化硅陶瓷纤维的制备方法
CN108085785A (zh) * 2018-01-15 2018-05-29 中钢集团洛阳耐火材料研究院有限公司 一种氮化硅纤维材料的制备方法
CN108328586A (zh) * 2018-03-01 2018-07-27 西安交通大学 一种可压缩回复的氮化硅气凝胶及其制备方法
WO2020046687A1 (en) * 2018-08-31 2020-03-05 3M Innovative Properties Company Additive manufacturing method for making non-oxide ceramic articles, and aerogels, xerogels, and porous ceramic articles
CN109553395A (zh) * 2018-12-28 2019-04-02 西安交通大学 一种陶瓷气凝胶的低成本制备方法
CN109704781A (zh) * 2018-12-28 2019-05-03 西安交通大学 一种氮化硅纳米带气凝胶及其制备方法
CN110982111A (zh) * 2019-12-16 2020-04-10 中国科学院苏州纳米技术与纳米仿生研究所 3d打印芳纶气凝胶、其制备方法及应用
CN111004541A (zh) * 2019-12-24 2020-04-14 中国科学院苏州纳米技术与纳米仿生研究所 二氧化硅气凝胶纤维的3d打印墨水及3d打印制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LEI SU ET AL: "Resilient Si3N4 Nanobelt Aerogel as Fire-Resistant and Electromagnetic Wave-Transparent Thermal Insulator", 《APPL. MATER. INTERFACES》 *
施利毅: "《多孔材料奇妙的微结构》", 31 January 2018, 上海科学普及出版社 *
赵志扬等: "具有可逆形变的弹性气凝胶研究进展", 《高分子材料科学与工程》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890425A (zh) * 2022-04-02 2022-08-12 西安交通大学 一种多级结构弹性碳化硅纳米线气凝胶及其3d打印制备方法和应用
CN114890425B (zh) * 2022-04-02 2023-12-19 西安交通大学 一种多级结构弹性碳化硅纳米线气凝胶及其3d打印制备方法和应用

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